Preparation of Intellingent Catalysts by Means of Layered Host Compounds Structurally Modified with Guest Molecules

合成了手性铑配合物和结构调谐客体嵌入蒙脱石的新型主客体催化剂（MMS），并观察到随着层间距和客体分子取向的不同，催化作用发生了剧烈变化。不同层间间距的多改性催化剂（MMS）的制备：以伯胺和季铵为结构调质剂（C_nH_<2n+2>NH_3^+(1 C_n), C_nH_<2n+2>） _2 （CH_3)_2NH_3^+(4 C_n)）修饰的蒙脱石，当n为10 ~ 18时，1 C_n的间隙（CS）为0.37 ~ 1.07 nm， 4 C_n的间隙为1.93 ~ 2.88 nm。(2)通过改变宿主分子的层电荷来控制客体分子的取向。(3) MMS催化前手性烯烃和酮的不对称加氢：在30 atm的H_2压力下，MMS催化剂对α -蒎烯和苯乙酮加氢的催化活性和选择性高于相应的均相催化剂。这些结果表明，MMS催化剂比均相催化剂更稳定。(4)影响层间间距和客人取向的催化行为:发现客人的层间间距和方向明显影响催化活性和选择性,在alpha-pinene的加氢,Rh-DIOP / C_nN ^ + / NaHT (c = 2.46 - -2.78海里)显示了转换低exo-selectivity 50 - 70的1.3 - -7.3% %,而Rh-DIOP / C_nN ^ + / LiTN (c = 1.93 - -2.88海里)显示更高的转化率超过99.8% exo-selectivity高92%。由于LiTN的层电荷密度比NaHT高3倍，因此在LiTN中结构调谐客体（C_nN^+）的取向几乎垂直于硅酸盐层，而在NaHT中结构调谐客体的取向在与层片的58 ~ 65度之间。特别是客体取向对催化活性和选择性有明显的影响。

The novel host-guest catalysts (MMS), in which chiral rhodium complexes as well as structural tuning guests were intercalated into smectites, were synthesized, and drastic change in catalysis was observed depending on the interlayer spacing as well as the orientation of guest molecules.Preparation of multiple-modified catalysts (MMS) with various interlayer spacings : Smectites modified with structural tuning guests such as primary and quaternary ammoniums (C_nH_<2n+2>NH_3^+(1ﾟC_n), (C_nH_<2n+2>) _2 (CH_3)_2NH_3^+(4ﾟC_n), respectively) have clearance spaces (CS) of 0.37 -1.07 nm for 1ﾟC_n and 1.93-2.88 nm for 4ﾟC_n with changing n from 10 to 18. (2)Control of the orientation of the guest molecules by changing the layer charge of hosts. (3)Catalysis for the asymmetric hydrogenation of prochiral olefins and ketones by MMS : MMS catalysts show higher catalytic activity and selectivity than the corresponding homogeneous ones in the hydrogenation of alpha-pinene and acetophenones at 30 atm of H_2 pressure. These results indicate that MMS catalysts are more stable than the homogeneous ones. (4)Effect of the interlayer spacing and the guest orientation on the catalytic behavior : It is found that the interlayer spacing and the orientation of guests clearly affect the catalytic activity as well as the selectivity, In the hydrogenation of alpha-pinene, Rh-DIOP/C_nN^+/NaHT(CS=2.46-2.78nm) showed the conversions of 1.3-7.3 % with low exo-selectivity of 50-70 %, while Rh-DIOP/C_nN^+/LiTN(CS=1.93-2.88nm) showed much higher conversions over 99.8 % with high exo-selectivity of 92 %. Since LiTN has three times higher layer charge density than NaHT, the orientation of structural tuning guests (C_nN^+) in LiTN was nearly perpendicular to the silicate layer, while that in NaHT was in the range between 58 to 65 degree to the layer sheet. Particularly these guest orientations definitely affect the catalytic activity and selectivity.